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EP1641735B1 - Procede pour produire des sels metalliques d'acides carboxyliques insatures a chaines courtes et utilisation de ces sels metalliques - Google Patents

Procede pour produire des sels metalliques d'acides carboxyliques insatures a chaines courtes et utilisation de ces sels metalliques Download PDF

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Publication number
EP1641735B1
EP1641735B1 EP04738847A EP04738847A EP1641735B1 EP 1641735 B1 EP1641735 B1 EP 1641735B1 EP 04738847 A EP04738847 A EP 04738847A EP 04738847 A EP04738847 A EP 04738847A EP 1641735 B1 EP1641735 B1 EP 1641735B1
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Prior art keywords
metal salts
formulation
metal
carboxyl group
reaction
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German (de)
English (en)
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EP1641735A2 (fr
Inventor
Peter Finmans
Detlef Hoell
Eveline Nickel
Elmar Gramse
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Sasol Solvents Germany GmbH
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Sasol Solvents Germany GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00

Definitions

  • the invention relates to a process for the preparation of metal salts of short-chain, unsaturated carboxylic acids by reacting unsaturated carboxylic acids with metal alcoholates.
  • the invention further relates to the use of metal salts of short-chain, unsaturated carboxylic acids.
  • Monosaturated carboxylic acids have in their homologous series the general empirical formula C n H 2n-1- COOH. They are colorless liquids which, at low chain lengths, are miscible with water in any proportion and tend to polymerize to a glassy mass.
  • the metal salts of acrylic acid are colorless. They can be prepared in solution and as a powder.
  • a metal salt of a carboxylic acid is formed by reacting a carboxylic acid with an activated metal.
  • the activated metal forms when a first metal is reacted with a second metal having hydrogen affinity in the presence of a proton source.
  • Activated aluminum from a highly purified aluminum rod is used and reacted with an alloy of gallium and indium in the presence of hydrochloric acid.
  • a disadvantage of this method is the need to use alloyed aluminum metal, wherein the components of the alloy are partly highly environmentally harmful and their recovery requires very complex separation techniques.
  • the US 3,923,716 describes the preparation of an aluminum acrylate in two steps. First, acrylic acid is added to aqueous sodium hydroxide solution to obtain sodium acrylate, which in turn is reacted with aluminum trichloride to form (mono-, di-, tri-) aluminum acrylate and sodium chloride. The aluminum acrylate can be separated from the dissolved sodium chloride due to its low solubility from the aqueous reaction mixture. A disadvantage of this method is that a large amount dissolved in water and partially contaminated with product cooking salt arises and must be disposed of.
  • Object of the present invention is to overcome the disadvantages described above, and in particular to provide a method in which exclusively safe and easily and completely separated by-products are formed and which is suitable for producing very pure carboxylic acid metal salts of various metal ions, preferably while avoiding the formation of unwanted polymeric compounds , and without the use of expensive additional purification steps can be performed.
  • the reaction is carried out in the presence of oxygen so that the reaction solution is at least 50%, preferably at least 90%, oxygen-saturated, for example by supplying a gas mixture, the oxygen in a concentration of 5 to 30 vol .-%, preferably 15 to 25 Vol .-% contains. Also suitable is the supply of oxygen in the form of an air mixture, especially when it has dried. The presence of oxygen suppresses the polymerization tendency of the product during production.
  • the process according to the invention takes place at temperatures of 0 ° C. to 150 ° C., preferably 20 to 100 ° C., more preferably at least temporarily above 40 ° C.
  • the invention preferably works at pressures of 2 bar abs to 0.01 bar abs .
  • the process may be solvent-free, i. apart from the above reactants, if necessary in excess, be carried out without additional solvents or diluents.
  • solvents are suitable hydrocarbons, esters, especially esters of C1 to C18 monocarboxylic acids with C1 to C8 alcohols and ether alcohols including polyols, ethers, glycols and / or glycol mono- / di-ether.
  • the reacted metal compounds are metal alkoxides according to the invention.
  • the bound metal ion is an ion of the metals magnesium, calcium, aluminum, silicon, tin, lanthanum, titanium, zirconium, copper and zinc, preferably aluminum, zirconium and titanium, in particular aluminum.
  • metal alkoxides according to the invention are aluminum tris- sec -butoxide, aluminum triisopropylate, zirconium tetrabutylate, titanium tetrabutoxide, magnesium dibutylate.
  • Particularly preferred metal alcoholates are alcoholates of alcohols having from 3 to 4 carbon atoms, such as isopropanol, n-butanol and sec. Butanol, especially isopropanol and sec. Butanol. Gff.
  • the alcohol group may also have been obtained from a polyol.
  • the most frequent fields of application of the metal compounds of unsaturated carboxylic acids according to the invention, in particular aluminum mono to tri (meth) acrylates, are the production of rubber materials, of synthetic resins and of flame retardants and for coatings and additives used in coatings ,
  • the coatings can be carried out on glasses, ceramics, organic polymers, metals, papers and cardboard.
  • metal (meth) acrylates are: Corrosion protection of metals, coating or production of glass fibers, sand cores, paper, plastics, etc., sheathing of (direct current) cables, additives to building materials and light-curing cements, photosensitive and light-sensitive imaging media and photographic paper coatings, polishes, stabilizers for polymers, removal of solids Water-based paints, rheology-improving and fungicidal additive and desiccant in the production of paints, inks and inks, and in medicine as the basis for gel patches or cements in dentistry.
  • Metal salts of short-chain, unsaturated carboxylic acids can be used in protective coatings of various natures.
  • resins such as alkyd, epoxy or acrylic-containing polymers, which may serve for the sealing of countertops made of marble or natural stone, parquet or fiberboard.
  • the resin gives the worktop a high resistance to aggressive and / or corrosive chemicals, as well as to mechanical and thermal stresses.
  • epoxy resins are combined with bitumen or asphalt to epoxy resin / tar coatings.
  • Polyurethane coatings are used in furniture, automobiles and aircraft.
  • Another field of application is the protective coating of concrete surfaces, marble statues and similar stone sculptures.
  • Phenolic resins have a high corrosion resistance and are thus used very often in the food packaging for cans.
  • Modified phenolic resins are used as antifouling paints for maritime applications and as a base for corrosion protection for sea and land vehicles.
  • metal salts of short chain unsaturated carboxylic acids improves e.g. the hardness, at the same time results in an improved protection against mechanical, thermal and chemical influences.
  • paints in which metal salts of short-chain, unsaturated carboxylic acids can be used according to the invention, lacquers, solvent and / or hydrous, z. B. alkyd resin, PU, NC, epoxy and acrylic resin.
  • alkyd resin PU, NC, epoxy and acrylic resin.
  • Such paints are used to seal materials such as metals, plastics, papers or cardboard and wood, and thus to protect them from decomposition or attack by aggressive environmental conditions. Examples include a rust-proof paint on a metal stair railing of an outside staircase or the protective coating for ships.
  • UV protective coatings for garden furniture, wood preservatives or impregnating varnishes for paper or cardboard work In an analogous way UV protective coatings for garden furniture, wood preservatives or impregnating varnishes for paper or cardboard work.
  • Acrylic resin paints are firstly used because of their rapid drying for painting plastics (phono / TV housings, toys, automotive interior parts) and secondly as chemically crosslinking coatings for high-quality non-yellowing weather-resistant coatings (2-component paints, facade paints, stoving enamels).
  • Air-drying alkyd resin coatings are used in principle for building coatings, but also for ships u. Machine colors, steel structures and used for the painting of large vehicles.
  • the uses for coating materials based on epoxy resins that cure at room temperature are very diverse. They are suitable for high-quality acid- and solvent-resistant coatings in areas that are not accessible to baked enamel, such as pipes, large containers, boats and hulls up to heavy corrosion protection.
  • Nitrocellulose lacquers are used in industrial furniture lacquering because they can be used transparently and opaque, both in the base coat and in the top coat. Nitrocellulose paints provide the best pore image and bring in especially open-pore varnish like no other material the wood character to advantage.
  • the coatings are fully resistant to moisture and sufficient against alcohol, but not against organic solvents. For engraving and offset printing inks, modified phenolic resins have great importance as binders. The solvent resistance and barrier properties of these coatings can be improved by the addition of metal acrylates.
  • the metal salts of short chain unsaturated carboxylic acids can also be used in polymer films of PP or PET, e.g. be used as packaging material to the object to be protected, glued or welded, are used.
  • polymer films of PP or PET e.g. be used as packaging material to the object to be protected, glued or welded, are used.
  • protective films for mobile phone displays or food are mentioned. Glassware exposed to high pressures and laminated glass panes are also protected from bursting by security films.
  • Metal salts of short-chain, unsaturated carboxylic acids can be used in addition to the organic coatings in inorganic protective coatings: z. B. this is done by vapor deposition of a metal layer on an object.
  • Such inorganic coatings is to form a metal oxide layer on metals or to apply such a metal oxide layer to a commodity, e.g. metallic or ceramic surfaces (including glass) may have.
  • a commodity e.g. metallic or ceramic surfaces (including glass) may have.
  • Aluminum is e.g. covered with an artificial oxide layer for protection. This process is called anodizing, or in general: anodizing.
  • this diffusion barrier is the following coating: It consists of an aluminum oxide layer applied between two acrylic acid polymer layers. This coating is intended to minimize oxygen transfer between the entrapped product and the environment.
  • Alumina is used in many of the above applications.
  • the disadvantage of alumina is that it is solid, insoluble and poorly reactive. It is usually not soluble in organic compounds, so that you need special equipment or implementations to incorporate this nevertheless.
  • the aim of the present invention is the advantageous use of metal salts of unsaturated carboxylic acids, which are versatile in substances or in combination with other materials alone or in mixtures, in liquid (dissolved) or solid form, are miscible / compatible with them and their reactive Groups can be polymerized or incorporated by combining the advantages of short-chain, unsaturated carboxylic acids with those of metal oxides and / or metal salts.
  • organic metal salts having at least one short-chain (3 to 7 carbon atoms), unsaturated carboxyl group are particularly well suited for subsequent uses:
  • the metal-organic compounds described can be used excellently in the surface coating.
  • these UV or electron beam coatings or coatings hardened by conventional chemical radical initiators also have good UV resistance and good adhesion to metals, mineral substrates and glass, as well as to a wide variety of organic polymer materials. These effects can be used advantageously even with the addition of small amounts of the organometallic compounds to organic coating materials (resins or monomers in general).
  • Metal alcoholates or metal salts such as with Ti, Zr or Si, result in coatings with the outstanding properties shown below.
  • Polymerization from a solution or emulsion makes it possible to produce polymeric particles. This succeeds, e.g. by UV-initiated suspension / emulsion / solution polymerization also from aqueous systems.
  • metal-organic compounds described can be used, for example, in sol-gel reactions, for example according to the reaction scheme below for the reaction of the compounds described using the example of Al acrylate:
  • the experiments were carried out in a 500 ml glass reaction flask equipped with a thermometer, a distillation head, dropping funnel, stirrer and gas inlet.
  • the first experimental example was carried out under nitrogen cover, the second under compressed air transmission.
  • the reaction vessel was cooled by means of a water bath.
  • the oxygen content of the supplied gas in Examples 2 to 7 was between 15 and 30% by volume (about 21% by volume).
  • the reaction mixture was oxygen saturated.
  • the flask was charged with 102.1 g of aluminum triisopropoxide, 120.1 g of diethylene glycol monobutyl ether, 0.7 g of 4-methoxyphenol, and 108 g of acrylic acid were added dropwise at room temperature (25 ° C.) over the course of 15 minutes by means of a dropping funnel.
  • the temperature increased by the heat of reaction to 53 ° C.
  • the mixture was cooled down to 39 ° C.
  • the product remained fluid and stable, so it could be treated as follows. It was heated to 60 ° C within 30 minutes, and driven off by means of a continuously adjusted vacuum to a value of 243 mbar within 2 hours, the co-product isopropanol.
  • the flask was charged with 509.3 g of zirconium tetra-butoxide, 498.6 g of diethylene glycol monobutyl ether and 2.8 g of 4-methoxyphenol. Then 382.7 g of acrylic acid were added dropwise quickly by means of a dropping funnel. The temperature rose to 45 ° C. The product remained liquid and stable and could therefore be heated to 90 ° C within 30 minutes. By means of a vacuum up to a value of 200 mbar, the co-product butanol was expelled within 1 hour.
  • Example 6 Preparation of a titanium tetra-acrylate in solution (not according to the invention)
  • the flask was charged with 510.6 g of titanium tetra-butoxide, 498.6 g of diethylene glycol monobutyl ether and 2.8 g of 4-methoxyphenol. Then 432.6 g of acrylic acid were added dropwise quickly by means of a dropping funnel. The temperature rose to 50 ° C. The product remained liquid and stable and could therefore be heated to 90 ° C within 30 minutes. By means of a vacuum up to a value of 200 mbar, the co-product butanol was expelled within 1 hour.
  • Example 7 Preparation of a magnesium diacrylate in solution (not according to the invention)
  • the flask was charged with 510.55 g of magnesium di-butoxide, 498.6 g of diethylene glycol monobutyl ether and 2.8 g of 4-methoxyphenol. Then 431.7 g of acrylic acid were added dropwise quickly by means of a dropping funnel. The temperature rose to about 48 ° C. The product remained liquid and stable and could therefore be heated to 90 ° C within 30 minutes. By means of a vacuum up to a value of 200 mbar, the co-product butanol was expelled within 1 hour.
  • the flask was charged with 204.2 g of aluminum triisopropoxide, to which was added 216 g of acrylic acid at room temperature (25 ° C) over 8 minutes in the manner described above.
  • the temperature rose by the heat of reaction to 32 ° C, and there was a white solid.
  • the heating of the rotary evaporator was turned on and gradually heated to 70 ° C.
  • the negative pressure was gradually adjusted to 24 mbar. In this way, the isopropanol was driven off and a white solid in powder form was obtained.
  • the flask was charged with 204.2 g of aluminum triisopropoxide, to which was added 72 g of acrylic acid at room temperature (25 ° C) over 8 minutes in the manner described above.
  • the temperature rose by the heat of reaction to 32 ° C, and there was a white solid.
  • the heating of the rotary evaporator was turned on and gradually heated to 70 ° C.
  • the negative pressure was gradually adjusted to 24 mbar. In this way, the isopropanol was expelled and the white solid was obtained in powder form.
  • Example 10 Preparation of a zirconium tetraacrylate, solvent-free
  • the metal salts of acrylic acid prepared in Examples 2 to 10 are colorless and almost odorless in contrast to the pungent-smelling acrylic acid.
  • Formulation 1 consists of 50% aluminum triacrylate and 50% butyl triglycol. The result was a clear, slightly yellowish, viscous liquid.
  • Formulation 2 consists of 50% aluminum trimethacrylate and 50% butyl triglycol. The result was a clear, slightly yellowish, viscous liquid.
  • Formulation 3 consists of 31% aluminum triacrylate, 45% n-butyl acrylate and 24% 2-propanol. The result was a clear, slightly viscous liquid.
  • Formulation 4 consists of 30% aluminum triacrylate, 32% 2-hydroxyethyl methacrylate and 38% 2-butanol. The result was a clear, slightly viscous liquid.
  • Formulation 5 consists of 35% aluminum trimethacrylate, 43% n-butyl acrylate and 22% 2-propanol. The result was a clear, slightly viscous liquid.
  • Formulation 6 consists of 21% aluminum triacrylate, 31% n-butyl acrylate and 48% hydroxyethyl methacrylate. The result is a clear, slightly viscous liquid.
  • Formulation 7 consists of 90% Formulation 3 and 10% tetra-n-butylzirconate. The result was a clear, slightly viscous liquid.
  • Formulation 8 consists of 70% Formulation 3 and 30% tetra-n-butylzirconate. The result was a clear, slightly viscous liquid.
  • Formulation 9 consists of 90% Formulation 3 and 10% tetra-n-butyl titanate. The result was a clear, slightly yellowish, slightly viscous liquid.
  • Formulation 10 consists of 70% Formulation 3, 30% tetra-n-butyl titanate. The result was a clear, slightly yellowish, slightly viscous liquid.
  • All formulations 1 to 10 still contain 3% by weight of photoinitiator (2,2-diethoxyacetophenone) and about 0.15-0.2% by weight of stabilizer (4-methoxy-phenol).
  • the scratch hardness according to Wolff-Wilborn (ISO 15184) was determined with the aid of pencils of different hardness.
  • the pencils were pulled over the sample surface with a slide, at the same angle, which exerts a constant force on different sample carriers.
  • the film hardness was determined by the two degrees of hardness at the border between writing and penetrating effect.
  • the pencil hedges varied from 6B to 9H.
  • formulation 3 achieved the best value on steel, glass, polypropylene and aluminum.
  • the scratch hardness of the formulations of formulation 3 on polypropylene and aluminum exceeded the value for uncoated material.
  • the coating with the acrylic paint gave the best result.
  • the scratch hardness according to Clemen (ISO 1518) describes the scratch stress by movement of the sample under a ball-shaped carbide tipped with a defined force (0-20 N).
  • the scratch hardness corresponds to the force required to completely scratch through the coating.
  • the reference acrylic acrylic paint had the best scratch resistance on steel and also achieved a good comparative value on aluminum.
  • the best scratch hardness on aluminum was shown in formulation 9.
  • the acrylic paint, formulation 3, formulation 6 and the UV-curable adhesive gel gave a low scratch hardness on polycarbonate bodies.
  • Formulation 3 and the UV adhesive gel achieved the best scratch hardness on glass.
  • Acrylic varnish, formulation 3 and formulation 6 only achieved a low scratch hardness on the polypropylene test specimen.
  • the damping of a pendulum swinging on the coating is evaluated according to the standard regulation.
  • the pendulum rested on two steel hemispheres, which are vibrated on the coating to be tested.
  • a high number of oscillations is synonymous with a high hardness.
  • Formulation 3 showed the highest pendulum hardness on glass, polycarbonate, steel and aluminum. On polypropylene, Formulation 6 and the acrylic finish achieved good results, while Formulation 3 resolved the sample size.
  • the cross-hatch was tested on films that were stored in a climatic room after UV curing for a period of seven days.
  • the UV adhesive gel and acrylic paint showed the best results on glass.
  • the acrylic varnish and the UV adhesive gel as well as the formulations 3 and 6 achieved the best results.
  • polypropylene only the film of the acrylic varnish achieved a good cross-hatch result.
  • Formulation 3 as well as the UV adhesive gel achieved very good results on steel, while the acrylic paint had a significantly poorer profile.
  • all tested formulations and reference substances showed very good film properties.
  • the abrasion resistance was tested with a commercially available scouring pad. For this, the sponge was stretched in a sledge, which was moved back and forth by machine. One cycle corresponds to a forward and backward movement of the carriage. The evaluation criterion was the number of cycles that the sponge was dragged over the film without destroying it. The test was carried out after max. 5000 cycles stopped. The weight of the sponge and the carriage was 134 g, this corresponds to a pressure of 4 g / cm 2 . The film thickness of the tested formulations and reference substances was 50 ⁇ m wet. The storage after UV curing was carried out under standard conditions.
  • Formulation 3 achieved abrasion resistance of> 5000 cycles for all the storage times tested.
  • the films had scuff marks, but were still intact.
  • Formulation 6 improved the abrasion resistance with increasing storage time.
  • the acrylic varnish lost its rub resistance with increasing storage time.
  • ⁇ b> ⁇ i> Table 11 ⁇ / i> ⁇ /b> cycles after 1 hour storage time cycles after 24 hours storage time cycles after seven days storage time acrylic paint (Air drying) 2400 3200 1500 UV adhesive gel > 5000 > 5000 > 5000 Formulation 3 > 5000 > 5000 > 5000 Formulation 6 840 1200 4500
  • the adhesion test by tearing tests was carried out according to the following method. Carefully degreased or sanded test specimens, so-called “dolly's” are glued to the film stored in the climatic chamber with a 2-component epoxy adhesive. Excess glue is removed. The curing time is 8 hours at 23 ° C. The tension applied to the adhered test stamp was continuously increased until the test specimen broke off (numerical determination of the adhesive strength). According to ASTM D 4541, at least three individual tests are required for a meaningful tearing-off experiment. The primary test result is the tensile stress readable at the slave pointer in N / mm, which led to the demolition.
  • the coatings with formulation 3 achieved the highest delamination values on steel, copper and polycarbonate. The values were reached after 1 day of storage after UV curing. On polypropylene and PVC, the coatings with the UV adhesive gel and formulation 3 did not differ from each other. On glass, the UV adhesive gel increased its value after storage for 7 days, while the values of formulation 3 fell off.
  • Printing resins require a precisely adjusted rheology in order to realize a printing process at high speed.
  • An important value in the determination of rheological data is the apparent viscosity.
  • the change in apparent viscosity of printing resin binders by the addition of different metal acrylate-containing formulations was determined.
  • the reference material used was an untreated printing ink binder and a binding agent mixed with DOROX D 515.
  • the water absorption of paper was tested with commercial grade paper. For this purpose, formulations 1, 3 and 6 were tested in a layer thickness of 50 ⁇ m (on both sides of the paper).
  • the reference material was untreated paper.
  • the papers were placed in a water bath one hour after the UV exposure, for 2 hours or 24 hours. In another study, the samples were placed in a water bath again for two or 24 hours 7 days after the UV exposure.
  • the water absorption was determined by differential weighing, the data are given in% water absorption
  • Formulation 3 formulation 6, formulation 1 and the UV adhesive gel were applied to glass in a layer thickness of 50 ⁇ m and UV-cured. After a storage time of 1 hour and 24 hours, the films were treated with the following chemicals treated: methyl ethyl ketone, 2-propanol, acetic acid, phosphoric acid, mineral oil and 30% sodium hydroxide. The chemicals worked on the films for a period of 2 hours.
  • the films of Formulation 3 were already after 1 hour storage time after UV curing resistant or partially resistant to methyl ethyl ketone, 2-propanol and mineral oil.
  • the UV adhesive gel and the formulation 6 reached this resistance only after a storage time of 24 h (with the exception that the film of the UV adhesive gel was also resistant to mineral oil after 1 h storage time).
  • the UV adhesive gel was partially resistant to 30% sodium hydroxide solution. None of the tested substances was resistant to acids.
  • a coating of sportswear with Formulation 3 was made to hydrophobize the fiber.
  • the sprayed water formed drops that remained on the surface of the fabric.
  • the untreated sport-functional fiber on the other hand, immediately absorbed the water.
  • the sport-functional fiber was washed with a soapy water, dried and re-sprayed after a storage time of 3 weeks. The result remained positive.

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  • Health & Medical Sciences (AREA)
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  • Adhesives Or Adhesive Processes (AREA)

Claims (20)

  1. Procédé de production de sels métalliques d'acides carboxyliques insaturés à chaînes courtes, par conversion
    - de composés d'alcoolates métalliques
    - avec des acides carboxyliques de formule générale

            CnH2n-1C(=O)OH

    avec la double liaison en position 2 ou 3, dans laquelle n vaut 2, 3, 4, 5 ou 6, et/ou de l'acide maléique,
    - en présence d'oxygène (O2), où l'on amène en continu de l'oxygène de sorte que la solution réactionnelle soit saturée en oxygène à au moins 50 %, et
    les sels métalliques présentent au moins un groupe de formule

            CnH2n-1C(=O)O- et/ou -OC(=O)CH=CHC(=O)O-(H)

    et les métaux suivants ou leurs mélanges

            Al, Si, Sn, La, Zr, Cu et/ou Zn.

  2. Procédé selon la revendication 1, caractérisé en ce que l'on amène en continu de l'oxygène de sorte que la solution réactionnelle soit saturée en oxygène à au moins 90%.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que les sels métalliques correspondent à la formule générale

            M(OOCCnH2n-1)a(R1)b

    et, par conversion d'un acide carboxylique insaturé, linéaire ou ramifié, de formule

            CnH2n-1-COOH,

    dans laquelle n vaut 2, 3, 4, 5 ou 6, avec la double liaison en position 2 ou 3, avec un composé métallique de formule générale

            M(R1)c

    et le cas échéant

            H(R1)

    dans laquelle
    a vaut au moins 1 ; b vaut 0, 1, 2 ou 3 et (a+b) et c représentent, indépendamment les uns des autres, un nombre entier de 2 à 4,
    M représente le métal selon la revendication 1,
    R1 représente un groupe alcoolate ayant un radical hydrocarbure en C1 à C6, où R1 est un groupe alcoolate saturé, linéaire ou ramifié, pouvant être produit à partir d'un alcool avec au moins un groupe -OH,
    ou
    Figure imgb0005
     avec R2 ou R3 égal à -CH3, -C2H5, -C3H7 ou -C4H9, et
    où n, R1, R2 et R3 peuvent être différents pour chaque a, b ou c et où au moins un R1 dans M(R1)c représente un groupe alcoolate avec un radical hydrocarbure en C1 à C6.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que la conversion s'effectue en présence d'oxygène amené en continu sous la forme d'un mélange gazeux, qui contient de l'oxygène en une concentration de 5 à 30 % en volume.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que la conversion s'effectue à des températures allant de 0°C à 150°C.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que la conversion s'effectue à des pressions de 2 barabs à 0,01 barabs.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que la conversion s'effectue sans solvant.
  8. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que la conversion s'effectue dans au moins un des solvants cités ci-après : hydrocarbures, esters, éthers, glycols et mono-/diéthers de glycol.
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'acide carboxylique est l'acide acrylique ou l'acide méthacrylique.
  10. Procédé selon l'une des revendications précédentes, caractérisé en ce que le métal M est l'aluminium et/ou le zirconium.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce que le composé métallique est un alcoolate métallique.
  12. Procédé selon l'une des revendications précédentes, caractérisé en ce que la conversion s'effectue en l'absence d'eau (taux inférieur à 100 ppm).
  13. Utilisation de sels métalliques pouvant être produits selon l'une des revendications 1 à 12, présentant au moins un groupe carboxyle insaturé avec 3 à 7 atomes de carbone dans le groupe carboxyle ou ses produits de conversion en tant que ou dans des revêtements et dans des matériaux caoutchouteux.
  14. Utilisation de sels métalliques pouvant être produits selon l'une des revendications 1 à 12 en tant que ou dans des matériaux de revêtement pour le revêtement du cuir, du verre, des céramiques, du papier, du carton, des matières plastiques, des métaux et des textiles.
  15. Utilisation de sels métalliques pouvant être produits selon l'une des revendications 1 à 12, présentant au moins un groupe carboxyle insaturé avec 3 à 7 atomes de carbone dans le groupe carboxyle comme monomère dans les procédés de polymérisation.
  16. Utilisation de sels métalliques pouvant être produits selon l'une des revendications 1 à 12, présentant au moins un groupe carboxyle insaturé avec 3 à 7 atomes de carbone dans le groupe carboxyle comme additif dans des compositions adhésives ou compositions plastiques durcissables aux rayonnements.
  17. Utilisation de sels métalliques pouvant être produits selon l'une des revendications 1 à 12, présentant au moins un groupe carboxyle insaturé avec 3 à 7 atomes de carbone dans le groupe carboxyle dans des compositions d'encre d'impression.
  18. Utilisation de sels métalliques pouvant être produits selon l'une des revendications 1 à 12, présentant au moins un groupe carboxyle insaturé avec 3 à 7 atomes de carbone dans le groupe carboxyle ou ses produits de conversion en tant que modificateurs de rhéologie.
  19. Utilisation de sels métalliques pouvant être produits selon l'une des revendications 1 à 12, présentant au moins un groupe carboxyle insaturé avec 3 à 7 atomes de carbone dans le groupe carboxyle ou ses produits de conversion en tant que ou dans des revêtements barrières pour des films contre la pénétration de l'oxygène et/ou de l'eau.
  20. Utilisation de sels métalliques pouvant être produits selon l'une des revendications 1 à 12 d'après au moins une des revendications 13 à 19, caractérisée en ce que les compositions mises en oeuvre contenant des sels métalliques renferment en outre :
    ■ 1 à 5 % en poids de photoinitiateurs, et/ou
    ■ 0,05 à 2 % en poids de stabilisants UV et/ou radicalaires.
EP04738847A 2003-07-03 2004-07-02 Procede pour produire des sels metalliques d'acides carboxyliques insatures a chaines courtes et utilisation de ces sels metalliques Expired - Lifetime EP1641735B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL04738847T PL1641735T3 (pl) 2003-07-03 2004-07-02 Sposób wytwarzania soli krótkołańcuchowych, nienasyconych kwasów karboksylowych z metalami i ich zastosowanie

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10330217A DE10330217B3 (de) 2003-07-03 2003-07-03 Verfahren zur Herstellung von Metallsalzen kurzkettiger ungesättigter Carbonsäuren und Verwendung der erhaltenen Metallsalze
PCT/DE2004/001414 WO2005005364A2 (fr) 2003-07-03 2004-07-02 Procede pour produire des sels metalliques d'acides carboxyliques insatures a chaines courtes et utilisation de ces sels metalliques

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EP1641735A2 EP1641735A2 (fr) 2006-04-05
EP1641735B1 true EP1641735B1 (fr) 2008-09-24

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US (1) US7943798B2 (fr)
EP (1) EP1641735B1 (fr)
JP (1) JP4722040B2 (fr)
KR (1) KR101090098B1 (fr)
CN (1) CN1832913B (fr)
AT (1) ATE409175T1 (fr)
AU (1) AU2004255297B2 (fr)
CA (1) CA2530723C (fr)
DE (2) DE10330217B3 (fr)
PL (1) PL1641735T3 (fr)
WO (1) WO2005005364A2 (fr)
ZA (1) ZA200600089B (fr)

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WO2006065660A2 (fr) * 2004-12-13 2006-06-22 Hybrid Plastics, Inc. Compositions contenant du metal
US8709705B2 (en) 2004-12-13 2014-04-29 Pryog, Llc Metal-containing compositions and method of making same
JP5140241B2 (ja) * 2005-11-09 2013-02-06 三井化学東セロ株式会社 ガスバリア性膜の製造方法
US8802346B2 (en) * 2008-08-07 2014-08-12 Pryog, Llc Metal compositions and methods of making same
CN101402649B (zh) * 2008-11-17 2011-03-23 湖南大学 脂肪酸异丙醇铝及其制备方法与应用
JP5213736B2 (ja) 2009-01-29 2013-06-19 パナソニック株式会社 半導体装置
US8642803B2 (en) 2010-03-03 2014-02-04 Basf Se Preparation of ethylenically unsaturated carboxylic salts by carboxylation of alkenes
WO2011107559A2 (fr) * 2010-03-03 2011-09-09 Basf Se Préparation de sels d'acides carboxyliques éthyléniquement insaturés par carboxylation d'alcènes
JP6590294B2 (ja) * 2014-10-28 2019-10-16 日油株式会社 チタン石けんの製造方法
EP3359548B1 (fr) 2015-09-29 2020-12-23 Pryog, LLC Compositions métalliques et leurs procédés de réalisation
CN106365687A (zh) * 2016-08-16 2017-02-01 佛山市彩贵新型材料有限公司 一种提高瓷砖耐磨的助剂及应用方法
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CN106278156A (zh) * 2016-08-16 2017-01-04 佛山市彩贵新型材料有限公司 一种增强助剂组合物
CN106278289A (zh) * 2016-08-16 2017-01-04 佛山市彩贵新型材料有限公司 一种陶瓷硬度助剂组合物

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Publication number Publication date
JP2007506648A (ja) 2007-03-22
WO2005005364A3 (fr) 2005-03-24
PL1641735T3 (pl) 2009-03-31
CA2530723C (fr) 2010-04-06
DE10330217B3 (de) 2004-12-09
JP4722040B2 (ja) 2011-07-13
AU2004255297B2 (en) 2010-05-13
CN1832913A (zh) 2006-09-13
WO2005005364A2 (fr) 2005-01-20
AU2004255297A1 (en) 2005-01-20
ZA200600089B (en) 2007-02-28
CN1832913B (zh) 2010-05-26
EP1641735A2 (fr) 2006-04-05
KR101090098B1 (ko) 2011-12-07
DE502004008122D1 (de) 2008-11-06
CA2530723A1 (fr) 2005-01-20
US20070287747A1 (en) 2007-12-13
KR20060028703A (ko) 2006-03-31
US7943798B2 (en) 2011-05-17
ATE409175T1 (de) 2008-10-15

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